The Role of Surface States in the Oxygen Evolution Reaction on Hematite

Hematite (α‐Fe₂O₃) is an extensively investigated semiconductor for photoelectrochemical (PEC) water splitting. The nature and role of surface states on the oxygen evolution reaction (OER) remain however elusive. First‐principles calculations were used to investigate surface states on hematite under photoelectrochemical conditions. The density of states for two relevant hematite terminations was calculated, and in both cases the presence and the role of surface states was rationalized. Calculations also predicted a Nerstian dependence on the OER onset potential on pH, which was to a very good extent confirmed by PEC measurements on hematite model photoanodes. Impedance spectroscopy characterization confirmed that the OER takes place via the same surface states irrespective of pH. These results provide a framework for a deeper understanding of the OER when it takes place via surface states.     

The Nonanuclear [Mo(IV){(CN)Fe(III)(3-ethoxy-saldptn)}8]Cl4 Complex Compound Exhibits Multiple Spin Transitions Observed by Mössbauer Spectroscopy

The hyperfine interactions at ¹⁸¹Ta ions on Fe³⁺ sites in α-Fe₂O₃ (hematite) were studied in the temperature range 11–1100 K by means of the perturbed angular correlation (PAC) technique. The ¹⁸¹Hf(β⁻)¹⁸¹Ta probe nuclei were introduced chemically into the sample during the preparation. The hyperfine interaction measurements allow to observe the magnetic phase transition and to characterize the supertransferred hyperfine magnetic field B_hf and the electric field gradient (EFG) at the impurity sites. The angles between B_hf and the principal axes of the EFG were determined. The Morin transition was also observed. The results are compared with those of similar experiments carried out using ¹¹¹Cd probe. ^aAlso at Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, Argentina.     

Highly Conformal Deposition of an Ultrathin FeOOH Layer on a Hematite Nanostructure for Efficient Solar Water Splitting

An ultrathin (ca. 2 nm) amorphous FeOOH overlayer was deposited conformally on a hematite nanostructure by a simple solution‐based precipitation method, to generate an oxygen evolution cocatalyst for efficient solar water splitting. This uniform and highly conformal coating of the ultrathin metal oxyhydroxide is rare and is distinguished from the layers prepared by other conventional methods. With the FeOOH overlayer as the cocatalyst, the water oxidation photocurrent of hematite increased by a factor of approximately two and the onset potential shifted in the cathodic direction by 0.12 V under 1 sun illumination. The enhanced performance was attributed to the improved water oxidation kinetics and the passivation of the surface states of the hematite.     

煤的挥发分对高磷鲕状赤铁矿直接还原焙烧的影响

在相同还原焙烧条件和等量添加剂下,系统研究了煤基还原剂中的挥发分对鄂西高磷鲕状赤铁矿在直接还原焙烧过程中对含铁和磷矿物的影响.通过XRD及SEM分析对煤基中挥发分的作用机理进行初步阐述.研究结果表明,煤的挥发分有利于铁回收率的提高,对降低铁产品中磷不利.经过类高温干馏的两种煤种的原煤作为还原剂时,焙烧产品新生成脉石矿物不同,并且原矿中鲕绿泥石和石英等会与含铁矿物发生复杂的化学反应,原矿中含磷矿物大部分仍以氟磷灰石形式存在,但少部分含磷矿物仍会参与还原焙烧的反应.     

A Titanium‐Doped SiOx Passivation Layer for Greatly Enhanced Performance of a Hematite‐Based Photoelectrochemical System

This study introduces an in situ fabrication of nanoporous hematite with a Ti‐doped SiO_x passivation layer for a high‐performance water‐splitting system. The nanoporous hematite with a Ti‐doped SiO_x layer (Ti‐(SiO_x/np‐Fe₂O₃)) has a photocurrent density of 2.44 mA cm^?2 at 1.23 V_RHE and 3.70 mA cm^?2 at 1.50 V_RHE. When a cobalt phosphate co‐catalyst was applied to Ti‐(SiO_x/np‐Fe₂O₃), the photocurrent density reached 3.19 mA cm^?2 at 1.23 V_RHE with stability, which shows great potential of the use of the Ti‐doped SiO_x layer with a synergistic effect of decreased charge recombination, the increased number of active sites, and the reduced hole‐diffusion pathway from the hematite to the electrolyte.     

高压辊磨机操作因素对粉碎产品粒度特性的影响

采用高压辊磨机破碎贫赤铁矿,分别研究了辊面速度、辊面压力、矿石含水率等操作因素对中料和边料产品粒度特性的影响.结果表明:增加辊面压力,中料和边料产品粒度变细,中料产品粒度分布更加集中,边料产品粒度分布更加均匀;提升一定的辊面速度,中料产品粒度变细,粒度分布更加集中,继续提升辊面速度,中料产品粒度特性无明显变化,辊面速度变化对边料产品粒度特性影响不明显;提高给料矿石的含水率,中料和边料产品细度变化不明显,中料产品粒度分布更加集中,边料产品粒度分布更加均匀.     

高磷鲕状赤铁矿还原焙烧及微生物脱磷试验

以湖北鄂西某高磷鲕状赤铁矿为研究对象,采用还原焙烧-弱磁选方法进行试验,并用黑曲霉对磁选后精矿进行微生物浸出脱磷研究.试验结果表明,正交实验得出各因素对精矿品位的影响顺序从大到小依次为焙烧温度、焙烧时间、还原剂比例、磨矿粒度.最佳焙烧-弱磁选条件为焙烧温度900℃、焙烧时间25 min、还原剂配比6％、磨矿粒度-0.074 mm95.08％,在此条件下获得精矿品位57.25％、回收率90.20％的较好的选别指标.黑曲霉对精矿中的磷元素具有较强的脱除能力,微生物浸出作用8d后,在较低的矿浆浓度下矿石的脱磷率为79.68％,矿石中的含磷量由0.85％降低到0.17％.该研究为微生物用于铁矿石的脱磷提供了理论依据.     

微波预处理条件对鄂西鲕状赤铁矿磨矿效率的影响

以鄂西鲕状赤铁矿为研究对象,采用不同功率与加热时间对其进行微波预处理,研究矿样在微波场中的升温特性,考察预处理前后矿样形貌、比表面积及孔隙率变化,分析所得矿样的磨矿效率、邦德磨矿功指数及过程功耗。结果表明,当微波功率为1~3kW时,矿石可在90s内被迅速加热至400℃以上,且升温速率随功率的增大而增加;经不同条件微波预处理后,赤铁矿与脉石颗粒间出现明显裂缝,矿石比表面积与孔隙率分别提升43.8%~51.9%和20.9%~40.0%;相同磨矿条件下,经功率为2kW、时间为45s处理后的矿样,-0.038mm和-0.074 mm粒级产品产率最高可提升37.2%和43.4%,邦德磨矿功指数最多可下降13.6%;微波预处理有助于降低磨矿过程功耗,当磨矿产品中-0.038 mm粒级产率为49.2%时,最大能耗降幅为21.4%。     

Effect and mechanism of siderite on reverse flotation of hematite

The effects of siderite on reverse flotation of hematite were investigated using micro flotation, adsorption tests, and Fourier transform infrared spectroscopy. The flotation results show that interactions between siderite and quartz are the main reasons that siderite significantly influences the floatability. The interactions are attributed to dissolved siderite species and fine siderite particles. The interaction due to the dissolved species is, however, dominant. Derjaguin-Landau-Verwey-Overbeek (DLVO) theoretical calculations reveal that adhesion on quartz increases when the siderite particle size decreases and that fine particles partly influence quartz floatability. Chemical solution calculations indicate that the dissolved species of siderite might convert the surface of active quartz to CaCO₃ precipitates that can be depressed by starch. The theoretical calculations are in good agreement with the results of adsorption tests and FTIR spectroscopy and explain the reasons why siderite significantly influences reverse flotation of hematite.